Coordination chemistry and hydrolysis of Fe(III) in a peat humic acid studied by X-ray absorption spectroscopy

The speciation of iron (Fe) in soils, sediments and surface waters is highly dependent on chemical interactions with natural organic matter (NOM). However, the molecular structure and hydrolysis of the Fe species formed in association with NOM is still poorly described. In this study extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry and hydrolysis of Fe(III) in solution of a peat humic acid (5010-49,200 μg Fe g⁻¹ dry weight, pH 3.0-7.2). Data were analyzed by both conventional EXAFS data fitting and by wavelet transforms in order to facilitate the identification of the nature of backscattering atoms. Our results show that Fe occurs predominantly in the oxidized form as ferric ions and that the speciation varies with pH and Fe concentration. At low Fe concentrations (5010-9920 μg g⁻¹; pH 3.0-7.2) mononuclear Fe(III)-NOM complexes completely dominates the speciation. The determined bond distances for the Fe(III)-NOM complexes are similar to distances obtained for Fe(III) complexed by desferrioxamine B and oxalate indicating the formation of a five-membered chelate ring structure. At higher Fe concentrations (49,200 μg g⁻¹; pH 4.2-6.9) we detect a mixture of mononuclear Fe(III)-NOM complexes and polymeric Fe(III) (hydr)oxides with an increasing amount of Fe(III) (hydr)oxides at higher pH. However, even at pH 6.9 and a Fe concentration of 49,200 μg g⁻¹ our data indicates that a substantial amount of the total Fe (>50%) is in the form of organic complexes. Thus, in environments with significant amounts of organic matter organic Fe complexes will be of great importance for the geochemistry of Fe. Furthermore, the formation of five-membered chelate ring structures is in line with the strong complexation and limited hydrolytic polymerization of Fe(III) in our samples and also agrees with EXAFS derived structures of Fe(III) in organic soils.     

Radioastronomical observations of comets IRAS-Araki-Alcock (1983d) and Sugano-Saigusa-Fujikawa (1983e)

Detections and upper limits to the continuum emission (1 ≤ λ ≤6 cm) and spectral line emission (OH, CO, CS, HCN, HCO⁺, CN, CH₃CN, CH₃C₂H, NH₃, H₂O, HC₃N, CH₃CH₂CN) are reported from radio observations of Comets 1983d and 1983e. Comparison is made with observations of CN at optical wavelengths. These results may be useful in planning future cometary observations.     

National forest carbon inventories: policy needs and assessment capacity

Previous research has identified the importance of the role of land cover in the global carbon cycle. In particular, forests have been identified as a significant carbon sink that can mitigate the rate of global climate change. Policy makers are faced with complex and difficult challenges in getting timely and useful information in monitoring global forest resources. Recent advances in the tools and methods of forest carbon accounting have produced new, innovative approaches to forest-based carbon inventories. But it is important as new tools are developed that scientists understand the needs of policy makers and that policy makers understand the capabilities and limitations of forest inventory methods. This paper explores four different policy applications that rely, or could benefit from, national carbon inventories. The goal is to help build a bridge between the communities of climate policy makers and scientists specialized in forest carbon inventories. To this end, we pursue three specific objectives: First we provide an overview for policy makers about approaches to forest carbon inventories, paying particular attention to the contributions of remote sensing technologies. Second, we outline the issues particularly relevant to forest inventory scientists who are interested in responding to public policy needs. We then discuss the tradeoffs between information cost, accuracy, precision, transparency and timeliness that need to be balanced in long-term monitoring of forest carbon. Finally, the article concludes with a series of observations and recommendations for the implementation of forest carbon inventories as increasingly central components of global climate change policy.     

Iron isotope variations in Holocene sediments of the Gotland Deep, Baltic Sea

Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in δ⁵⁶Fe (differences in the ⁵⁶Fe/⁵⁴Fe ratio relative to the IRMM-14 standard) from −0.27 ± 0.09‰ to +0.21 ± 0.08‰. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean δ⁵⁶Fe of +0.08 ± 0.13‰, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean δ⁵⁶Fe of −0.14 ± 0.19‰. Negative correlations of the δ⁵⁶Fe values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of −1.06 ± 0.20‰ for δ⁵⁶Fe. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved δ⁵⁶Fe value of about −1.4‰ to −0.9‰. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive δ⁵⁶Fe values.